Synthesis of Functionalized 1,3,2-Benzodiazaborole Cores Using Bench-Stable Components

Davies, Geraint H. M.; Molander, Gary A.

doi:10.1021/acs.joc.6b00435

Cited by 20 publications

(17 citation statements)

References 42 publications

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“…Both the centers of the rings (0.0 Å) and the points off the ring centers (1.0 Å) are in the perpendicular direction (Supporting Information, Figures S11, S12) and the corresponding NICS values are listed in Table . All five‐membered BN/CC analogs studied exhibit negative NICS values, indicating their aromaticity, but all six‐membered BN/CC analogs have positive NICS values, indicating that these six‐membered rings are anti‐aromatic . All these NICS results are consistent with the electrostatic potential and π‐electron results reported above, and indicate significant differences in aromaticity between these five‐ and six‐membered conjugated diazaborinine rings.…”

Section: Methodssupporting

confidence: 85%

“…All five-membered BN/CC analogs studied exhibit negative NICS values,indicating their aromaticity,but all six-membered BN/CC analogs have positive NICS values, indicating that these six-membered rings are anti-aromatic. [9] All these NICS results are consistent with the electrostatic potential and p-electron results reported above,and indicate significant differences in aromaticity between these five-and six-membered conjugated diazaborinine rings.…”

Section: Samplesupporting

confidence: 88%

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NBN‐Doped Conjugated Polycyclic Aromatic Hydrocarbons as an AIEgen Class for Extremely Sensitive Detection of Explosives

et al. 2018

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As imple and efficient synthesis of NBN-doped conjugated polycyclic aromatic hydrocarbons (sucha sd iazaborinines) has been accomplished by ac atalyst-free intermolecular dehydration reaction at room temperature between boronic acid and diamine moieties with yields up to 99 %. Polycyclic aromatic hydrocarbons with as ix-membered NBN ring are an ew class of aggregation-induced emissive luminogens.E xtremely sensitive detection of ppb levels of TNT by phenyl naphthodiazaborinine is straightforward. Visual detection of TNT is illustrated by fabrication of TNT test strips, which can detect as little as 100 ng of TNT powder.This simple and sensitive detection of TNT has potential applications in the area of public safety and security against terrorist activities.Doping of polycyclica romatic hydrocarbons (PAHs) with boron-nitrogen units,t hat is,i soelectronic and isosteric replacement of aC =Cb ond with aB ÀNb ond (Scheme 1), has emerged as av ersatile strategy for the preparation of novel hybrid PA Hs with unusual and attractive optical, electronic,a nd chemical properties that are absent from their C=Cc ongeners. [1] Them olecular design of boronnitrogen-doped PA Hs therefore expands the structure and functionality library of p-systems,and such chemistry is highly desirable in the development of useful materials. [2] For example,since the pioneering work on BN doped p-systems, namely azaborinines,b yD ewar and White in the 1960s, considerable research effort has been devoted by,for example Ashe,L iu, Braunschweig,S chäfer,a nd Jäkle [3] to the synthesis,p roperties,a nd reactivity of azaborinines.S ince Weberspioneering work on NBN-doped compounds,specifically diazaborinines,t here have been numerous investigations of their synthesis,o na ccount of their potential applications as drugs and as reagents that can be used in the Suzuki-Mayaura reaction. [4] Although considerable progress has been made in boron-nitrogen doped p-systems,t he currently available preparative methods suffer from the need for rigorous reaction conditions including the requirement for conditions which are air-and/or moisture-free,multiple steps and unsatisfactory total yield. Finding as imple and mild strategy with which to synthesize boron-nitrogen-doped PA Hs is therefore significant and highly desirable.Boron-containing p-systems have attracted considerable research attention since the 1960s due to their desirable optical, electronic, and sensory properties. [5] With the presence of an empty porbital of the boron center in p-systems, such compounds are luminogens and are widely utilized as such. [6] Tr aditional luminogens fluoresce strongly in dilute solution but are subject to aggregation-caused quenching (ACQ) [7] and the luminogens are quenched at higher concentrations or in aggregation states.I n2 001, Tang described the aggregation-induced emission (AIE) of luminogens (AIEgens), [8] which fluoresce weakly when dissolved, but emit strongly when aggregated. As an important class of luminogens,b oron containing p-systems featuring AIE,...

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Section: Methodssupporting

confidence: 85%

Section: Samplesupporting

confidence: 88%

NBN‐Doped Conjugated Polycyclic Aromatic Hydrocarbons as an AIEgen Class for Extremely Sensitive Detection of Explosives

et al. 2018

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“…[7] The best-studied NÀBÀNm otif, 1,3,2-diazaborole, represents ac lass of five-membered heterocycles that are isosteric with pyrroles ( Figure 1A). [8][9][10] In addition to their attractive properties as ligands and for electrochemistry,t hesec ompounds often exhibite xtremely high luminescence quantum yields both in solution and in the solid state. Ar ecent paper by Wan and co-workers compared 1,3,2-benzodiazaboroles with their six-memberedr ing counterparts, naphthodiazaborines( BDANs) ( Figure 1B).…”

mentioning

confidence: 99%

Diazaboryl‐naphthyl‐ketone: A New Scaffold with Bright Fluorescence, Aggregation‐Induced Emission, and Application in the Quantitation of Trace Boronic Acids in Drug Intermediates

Hackney

Paladino

et al. 2020

Chemistry A European J

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This study describes the synthesis, structure, and photophysical properties of an ew luminescent polyaromatic boronic acid scaffold, diazaboryl-naphthyl-ketones (DNKs). These stable compounds display extremely bright fluorescence, aggregation-inducede mission, positive solvatochromism,a nd solid-statef luorescence. DFT calculations and X-ray crystallographic study revealed notable electronic and structurald ifferences between these compounds and the parentd iaminonaphthalene (DAN) adducts. Acylation of the DAN system causes alocalization of both HOMO and LUMO onto the DNK unit, which validates the negligible influenceo ft he B-aryl substituent. The LUMO energy is lowered, and its shape significantly altered.P hotophysical data in solution and the solids tate revealedb lue-shifted, narrowed, and intense emissions for DNKs (up to 89 %q uantum yield). The potentialu tility of the fluorogenic DNK system was demonstrated with a proof-of-concept for the determination of trace boronic acid contaminants in solid samples, down to one-ppm level, using HPLC with fluorescence detection. This methodc ould be useful in pharmaceutical development for the quantitationo fd ifficult-to-detect and potentially mutagenic residual boronic acid from late cross-coupling reactions in drug syntheses.

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“…In 2016, the Molander group reported a new method for the synthesis of 1,3,2-benzodiazaboroles using benchstable starting materials. 57 Reaction of functionalized 1,2phenylenediamine 88 with (hetero)aryl-, alkyl-, alkynyland alkenyltrifluoroborates 89 in the presence of boron trifluoride-ethylamine complex afforded the corresponding 1,3,2-benzodiazaborole derivatives 90 (Scheme 29). Computational studies support the aromatic character of those products 90.…”

Section: Scheme 26 Synthesis Of the Parent 132-benzodiazaborolementioning

confidence: 99%

Construction of Boron-Containing Aromatic Heterocycles

Kinjo

2017

Synthesis

113

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Boron-containing aromatic systems exhibit unique electronic properties and reactivities that have been extensively studied for a long time. This review highlights the recent developments in the synthesis of aromatic boron-containing heterocycles. The organization of the contents is based on the sizes of rings and the heteroatoms other than boron. Early work in the field is briefly introduced, but the main focus is on recent reports published during the period of 2008 through 2016.1 Introduction2 Five-Membered Rings2.1 Borole Derivatives2.2 B,N-Heterocycles2.3 B,O-Heterocycles3 Six-Membered Rings3.1 Borabenzene Derivatives3.2 Boratabenzene Derivatives3.3 1,4-Diborabenzene3.4 B,N-Heterocycles3.5 B,E-Heterocycles (E = O, S, P, Te)4 Three-Membered Rings4.1 Borirenes4.2 Azadiboriridines4.3 Triboracyclopropenyl Dianion5 Four-Membered Rings5.1 bicyclo-Tetraborane(4)5.2 1,3-Diborete5.3 B,E-Heterocycles (E = N, P, As, Sb, Bi, O, S, Se)6 Seven-Membered Rings (Borepines)7 Conclusion and Perspective

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Synthesis of Functionalized 1,3,2-Benzodiazaborole Cores Using Bench-Stable Components

Cited by 20 publications

References 42 publications

NBN‐Doped Conjugated Polycyclic Aromatic Hydrocarbons as an AIEgen Class for Extremely Sensitive Detection of Explosives

NBN‐Doped Conjugated Polycyclic Aromatic Hydrocarbons as an AIEgen Class for Extremely Sensitive Detection of Explosives

Diazaboryl‐naphthyl‐ketone: A New Scaffold with Bright Fluorescence, Aggregation‐Induced Emission, and Application in the Quantitation of Trace Boronic Acids in Drug Intermediates

Construction of Boron-Containing Aromatic Heterocycles

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